Copolymers of substituted 1,3-dioxepins



United States Patent 3 219 629 COPOLYMERS on srinsfrruruo 1,3-DIOXEPINS George B. Sterling, Midland, Mich, assignor to The Dow Chemical Company, Midland, Mich, a corporation of Patented Nov. 23, 1965 ice These 1,3-dioxepins may be homopolymerized or copolymerized with other monomers such as vinyl aromatic compounds, i.e. styrene, dichlorostyrene, t-butyl styrene, vinyl xylene, vinyl toluene, and the like, acrylic and meth- Deiaware 5 acrylic acid esters such as methyl methacrylate, ethyl hexyl N0 Drawing Fn Jam 3, 1961, Sen N 80,063 acrylate, ethyl acrylate, and the like, vinylidene chloride, 9 Claims. 31, 259 3 vinyl chloride, acrylonitrile, methyl isopropenyl ketone, butadiene, mixtures thereof and the like. When binary The present invention relates to organic resinous matecopolymers are prepared advantageous products are obrials, and is more particularly concerned with polymeric 10 tained by copolymerizing from 5 to 80 weight percent of and copolymeric compositions of matter containing at the substituted l,3-dioxepin with, correspondingly, from least one substituted 1,3-dioxepin in chemically combined 95 to 20 Weight percent of the desired monomer. When form, and with a method of making the same. ternary and quaternary copolymers are prepared advan- I have found that monomeric materials having the tageous products are obtained by copolymerizing desired formula mixtures containing from about 5 to about 50 weight per- H H cent of the 1,3-dioxepin. The polymerization may be carried out in the usual 1129/ manner using persulfate, peroxide, 2120 and the like catalysts in mass or emulsion polymerization and in the presence of conventional suspending or emulsifying agents such as, for example, sodium lauryl sulfate and the like. 3 The present invention is further illustrated by the folwherein R and R represent individual members of the lgwmg examples but 18 not to be construed as hmlted group consisting of alkyl and halosubstituted alkyl groups P t ereto' EXAMPLE 1 containing from 1 to 9 carbon atoms, alkenyl groups containing from 2 to 9 carbon atoms, hydrogen, aryl groups Mixtures of 110 grams Water, 100 grams of mixed of the benzene series and R and R collectively represent monomers, 0.85 gram of sodium lauryl sulfate, 1.0 gram the divalent group each of sodium bicarbonate and tertiary dodecyl mer- CHPCHP captan, and potassium persulfate as shown in the follow- H C ing table, were polymerized at a temperature of C., 2 for the times and with the results shown in Table I. The

CH2 C}I2 crude products were steam distilled to remove unpolymmay be polymerized or copolymerized ith oth erized monomer. In some cases, as shown in the table, polymerizable monomers, using conventional mass, emul- 35 an antlfvfldant was d d Alumlullru u fate W218 u d sion or suspension polymerization techniques to produce to Preclpltate the Polymfir after Whlch It Was Washed and new polymeric and copolymeric materials which can be dried. The resulting products had good elongation tenextruded or molded in usual ways employing conven sile and notched impact strength, and were readily molded tional procedures to form shaped articles such as boxes, into useful shapes and articles.

Table I 2,2-dimethyl- Percent Percent Percent Tert Percent 2,4- Rnn 4,7-dihydro- Percent Percent methyl ethyl odecyl Percent dirnethyl 6(1- Reaction Percent 1,3-dioxepin butadienc styrene isopropenyl aerylate mercaptan K2820; methylcyclotime, hrs. conversion etone hexyl) phenol .75 a 24 .75 a 24 82 .75 3 24 42 .75 3 24 as .7'5 3 24 2a .75 3 24 1s .5 3 so an .5 3 30 82 .5 3 30 44 .5 3 30 46 .75 3 24 90 .75 3 24 86 .75 a 24 24 24 24 so 24 so 24 86 24 24 24 9s 24 e7 24 30 plates, or plastic tags. They can also be incorporated with other resinous polymers to form compositions useful in making shaped articles, e.g. cups, tags, rings, etc.

Substituted 1,3-dioxepins which are useful in making the polymeric materials of the present invention include, for example, 2,2-dimethyl-4,7-dihydro-1,3-dioxepin; 7,12- dioxaspiro-[5.6] -dodec-9-ene; 4,7-dihydro-1,3-dioxepin; 2- ethyl-2-methyl-4,7-dihydro-1,3-dioxepin; 2,2 diethyl 4,7- dihydro-1,3-dioxepin; 2-methyl-2-propyl-4,7 dihydro-1,3- dioxepin; 2-methyl-4,7-dihydro-1,3dioxepin; and the like.

One hundred parts of the copolymer from Run 1 were compounded with 40 parts carbon black, 5 parts zinc oxide, 2 parts sulfur, 3 parts benzothiazyl disulfide and 1 part stearic acid and cured at 292 F. for 30 minutes. The resulting product had the following physical properties:

Tensile strength p.s.i 460 Elongation percent Permanent set do 3.0 Shore A hardness 48.0

Shore C hardness 7.5

An identical blend, except for using 100 parts of the copolymer from Run 2 andra curing time of 50 minutes at 292 F. gave a product with the following properties:

I 4 EXAMPLE 3 Following the procedure of Example -1, ternary polymers were prepared with 2,2-dimethyl-4,7-dihydro-1,3-dioxepin and other monomers as shown in the following table. One hundred parts of the products were compounded with 40 parts carbon black, parts zinc oxide, 2 parts sulfur, 3 parts benzothiozyl disulfide and 1 part stearic acid and then cured at 292 F. for 50 minutes. The physical properties given in the following table were Injection moldings 0f t e re nous products of Runs taken on the compounded and cured products.

Table III Weight Percent Tensile, Percent Percent Shore A Shore 0 Run Monomers percent conversion p.s.1. elongation permatnent hardness hardness 1 l fii d lefififiifitfi }.ii ffiif" i3 74 755 350 6.2 47 11 2 sattri etsttis iin $8} 80 508 270 0 50 17 3 giitidiiiie i3 52 898 400 3.1 45 4 3 ii t ;C 1 i e n e s 92 858 360 0 45 15 5 iifiihiigf f" g3 78 010 340 o 55 2o 6 firii iii ii ij $3 82 855 210 o 57 22 7 Butarlipne 50 g gt hgl e rzlate 33 i 68 594 280 1.5 47 n 9 thyaor ylate 80 524 170 0 52 u 2 IP m gu l m i ether i 20 274 90 3.1 62 27 ll 11 gtlytliyilyl ether i 62 283 170 0 57 u a re e.

Diehlorostyrene 15 86 830 490 1-5 47 20 14, 15 and 16 at 410-420 F. and 350 to 400 p.s.i.g. re- EXAMPLE4 sulted in products having the following properties:

Following the procedure of Example 1 mixtures of 70 g zg fig 3 3 g zg gg 4 weight percent butadiene and weight percent of various substituted 1,3-dioxepins were polymerized in the presgggg 8-8 ence of 0.5 weight percent tertiary dodecyl mercaptan. 3: 100 4.2 0. 578 The results are given in the following table.

EXAMPLE2 In a manner similar to that of Example 1, 2,2-dimethyl- 4,7-dihydro-l,3-dioxepin was homopolymenzed and po- Table IV lymerized with varying weight percentages of other monomers as shown to produce polymeric products ranging from clear to opaque, insoluble in Skellysolve IOU-140 Run M n m r CPercent C., soluble to insoluble in methyl ethyl ketone and tolu- Onversmn e and havmg g p y P p S L ,lfldmydmlsdioxepin 64 Table II 2 2-methyl-2 ethyl-4,7-dihydro-L3-dioxep so 8. 2,2-diethyl-4,7-dihydrol,3-dioxepin 76 4- 2 methyl 2-propyl 4,7-dihydro-1,3-dioxe 84 Run Second monomer Weig Percellt 5. 7 ,12-dioxaspiro-[5.61dodec-9-ene 98 percent conversion 6 2-ethyl-4,7-dihydro-l,3-di0xepin 31 7. 2-propyl-4,7-dihydro-l,3-dioxep 8. 2-(3-butenyl) -2-methy1-4,7-dihydro- 71 8 9 a 'th 1 14 7 d h d 3 rornorne yI-Z-meti i ro-l, 80 3 95 92 6O dioxepin. y y 4 n 20 50 10 2-phenyl-4,7-dihydro-1,3-dioxepin 77 5 Methyl isopropenyl ketone 95 90 6 Vinylidene chloride 95 94 77,.-- rln 75 72 s 50 52 2 5 :36 0 6 50 60 95 3 These copolymers were soft-sticky materials insoluble 0 $8 fig in methyl ethyl ketone. 28 12 One hundred parts of the copolymers from Runs 6 58 g 70 through 13 inclusive were individually compounded with H g8 g8 40 parts Pelletex, 5 parts zinc oxide, 2 parts sulfur, 2 parts 2 vinyfpropionatau 28 2% Captax and 20 parts of dibutyl sebacate and then cured a 221:: l lone (homopollymer) 20 at 292 F. for 40 mmutes. The resulting products had Table V Copolymer 100% 300% Tensile, Percent Percent per Shore A Shore from Run modulus modulus p.s.i. elongation manent set hardness hardness EXAMPLE 5 vinyl and vinylidene chlorides, acrylonitrile, and mix- Mixtures of 20 weight percent 2,2-dimethyl-4,7-dihydro-1,3-dioXepin with other monomers were mass polymerized in the presence of two weight percent oc,oc-aZ0biS isobutyronitrile at 60 C. for 30 hours. The results are indicated in the following table.

T able VI Weight Percent Run Monomer percent conver- Properties I sion i 1 Acrylonitrile 801 66 Hard, insoluble.

iAcrylonitri e- 40 2 Styrene 4D) 88 3 Ethyl acrylate 80 100 Soft, sticky rubber.

Various modifications may be made in the present invention Without departing from the spirit or scope thereof, and it is understood that 1 limit myself only as defined in the appended claims.

What is claimed is:

1. Organic polymeric products consisting essentially of copolymers of from 5 to 80 weight percent of a dioxepin having the formula and correspondingly from 95 to 20 weight percent of a monomer selected from the group consisting of vinyl aromatic compounds, acrylic and methacrylic acid esters,

tures of said monomers.

2. Product of claim 1 wherein the vinyl aromatic compound is styrene and the dioxepin is 2,2-dimethyl-4,7- dihydro-1,3-dioxepin.

3. Product of claim 1 wherein the dioxepin is 2,2-dimethyl-4,7-dihydro-1,3-dioxepin and the second monomer is butadiene.

4. Product "of claim 1 comprising a copolymer of 2- ethyl hexyl acrylate and 2,2-dimethyl-4,7-dihydro-1,3- dioxepin.

5. Product of claim 1 comprising a copolymer of methyl isopropenyl kctone and 2,2-dimethyl-4,7-dihydro-1,3- dioxcpin.

6. Product of claim 1 comprising a terpolymer of from about 15 to 25 weight percent 2,2-dimcthyl-4,7- dihydro-1,3-dioxepin, about 15 to 25 weight percent styrene and from about 50 to weight percent butadiene.

7. Product of claim 1 comprising a terpolymer of from about 15 to 25 weight percent 2,2-dimethyl-4,7-dihydro- 1,3-dioxepin, 15 to 25 weight percent ethyl acrylate and about 50 to 70 weight percent butadiene.

8. A copolymer of butadiene and 2-(3-butenyl)-2-methyl-4,7-dihydro-1,3-dioxepin.

9. A cop'olyrner of butadiene and 2-bromomethy1-2- methyl-4,7-dihydro-1,3-dioxepin.

References Cited by the Examiner UNITED STATES PATENTS 2,578,861 12/1951 Thomas et a1. 260-883 2,870,097 1/1959 Pattison 2602 OTHER REFERENCES Chemical Abstracts, vol. 49, page LEON I. BERCOVITZ, Primary Examiner.

HAROLD N. BURSTEIN, JOSEPH R. LIBERMAN,

Examiners. 

1. ORGANIC POLYMERIC PRODUCTS CONSISTING ESSENTIALLY OF COPOLYMERS OF FROM 5 TO 80 WEIGHT PERCENT OF A DIOXEPIN HAVING THE FORMULA 